U.S. patent application number 17/414534 was filed with the patent office on 2022-02-17 for photochromic composition.
This patent application is currently assigned to THE PILOT INK CO., LTD.. The applicant listed for this patent is THE PILOT INK CO., LTD.. Invention is credited to Yasuaki KAMBE.
Application Number | 20220049103 17/414534 |
Document ID | / |
Family ID | |
Filed Date | 2022-02-17 |
United States Patent
Application |
20220049103 |
Kind Code |
A1 |
KAMBE; Yasuaki |
February 17, 2022 |
PHOTOCHROMIC COMPOSITION
Abstract
Disclosed is a photochromic composition comprising a
naphthopyran-based photochromic compound having a specific
structure and an oligomer.
Inventors: |
KAMBE; Yasuaki; (Nagoya-shi,
Aichi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
THE PILOT INK CO., LTD. |
Aichi |
|
JP |
|
|
Assignee: |
THE PILOT INK CO., LTD.
Aichi
JP
|
Appl. No.: |
17/414534 |
Filed: |
December 6, 2019 |
PCT Filed: |
December 6, 2019 |
PCT NO: |
PCT/JP2019/047972 |
371 Date: |
June 16, 2021 |
International
Class: |
C09B 67/20 20060101
C09B067/20; C09K 9/02 20060101 C09K009/02; C08L 23/06 20060101
C08L023/06; C08L 77/00 20060101 C08L077/00; C09D 5/29 20060101
C09D005/29; C09D 125/08 20060101 C09D125/08; C09D 133/04 20060101
C09D133/04; C09D 11/50 20060101 C09D011/50; C09D 11/18 20060101
C09D011/18; C09D 11/17 20060101 C09D011/17; C09D 11/037 20060101
C09D011/037; C09D 11/106 20060101 C09D011/106 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 27, 2018 |
JP |
2018-244604 |
Claims
1-18. (canceled)
19. A photochromic composition comprising a photochromic compound
represented by the following general formula (1) and an oligomer:
##STR00005## wherein, in the general formula (1), X.sup.1 and
X.sup.2 represent an oxygen atom, Y.sup.1 and Y.sup.2 represent CH,
R.sup.1 to R.sup.4 represent the general formula (2), R.sup.11 to
R.sup.14 represent a hydrogen atom, a halogen atom, a hydroxyl
group, a nitrile group, an alkyl group, an aryl group, an alkoxy
group, an aryloxy group, an acyl group, an alkoxycarbonyl group or
an aryloxycarbonyl group, R.sup.15 represents an alkyl group having
3 or more carbon atoms, * represents a binding site to a pyran
skeleton, and X.sup.1 and Y.sup.1, and X.sup.2 and Y.sup.2 are each
bonded to adjacent carbon atoms of the carbon atoms constituting a
naphthalene skeleton.
20. The photochromic composition according to claim 19, wherein the
general formula (1) is any one of the following general formulas
(3) to (9). ##STR00006## ##STR00007##
21. The photochromic composition according to claim 19, wherein the
general formula (1) is any one of the general formulas (5) to
(9).
22. The photochromic composition according to claim 19, wherein
R.sup.15 is an alkyl group having 3 or more and 8 or less carbon
atoms.
23. The photochromic composition according to claim 20, wherein
R.sup.15 is an alkyl group having 3 or more and 8 or less carbon
atoms.
24. The photochromic composition according to claim 21, wherein
R.sup.15 is an alkyl group having 3 or more and 8 or less carbon
atoms.
25. The photochromic composition according to claim 19, wherein the
oligomer is an oligomer selected from a styrene-based oligomer
having a weight-average molecular weight of 200 to 6,000, an
acrylic oligomer having a weight-average molecular weight of 12,000
or less, a terpene-based oligomer having a weight-average molecular
weight of 250 to 4,000 and a terpenephenol-based oligomer having a
weight-average molecular weight of 200 to 2,000.
26. The photochromic composition according to claim 25, wherein a
weight ratio of the photochromic compound to the styrene-based
oligomer or the acrylic oligomer is in the range of 1:1 to
1:10000.
27. The photochromic composition according to claim 25, wherein a
weight ratio of the photochromic compound to the terpene-based
oligomer is in the range of 1:1 to 1:5000.
28. The photochromic composition according to claim 25, wherein a
weight ratio of the photochromic compound to the
terpenephenol-based oligomer is in the range of 1:1 to 1:50.
29. The photochromic composition according to claim 19, wherein the
photochromic compound and the oligomer are encapsulated in
microcapsules or dispersed in resin particles.
30. The photochromic composition according to claim 20, wherein the
photochromic compound and the oligomer are encapsulated in
microcapsules or dispersed in resin particles.
31. The photochromic composition according to claim 21, wherein the
photochromic compound and the oligomer are encapsulated in
microcapsules or dispersed in resin particles.
32. The photochromic composition according to claim 19, further
comprising an ultraviolet absorber.
33. The photochromic composition according to claim 32, further
comprising a hindered amine-based light stabilizer.
34. A photochromic liquid composition comprising the photochromic
composition according to claim 19 and a vehicle.
35. The photochromic liquid composition according to claim 34,
which is selected from printing inks, inks for writing instruments,
inks for applicators, inkjet inks, paints, ultraviolet curable
inks, drawing colors, cosmetics and fabric-coloring fluids.
36. A photochromic molding resin composition comprising the
photochromic composition according to claim 19 and a molding
resin.
37. A photochromic molded body obtained by molding the photochromic
molding resin composition according to claim 36.
38. A photochromic laminated body comprising a support and a
photochromic layer containing the photochromic composition
according to claim 19 provided on the support.
39. An article using the photochromic composition according to
claim 19.
40. The article according to claim 39, which is a toy, a packaging
container, an embroidery thread or an indicator.
Description
TECHNICAL FIELD
[0001] The present disclosure relates to a photochromic
composition. More particularly, the present disclosure relates to a
photochromic composition using a naphthopyran-based photochromic
compound, which develops an orange to red color at the time of
coloration and can adjust the discoloration sensitivity, and also
exhibits high density in a colored state and little residual color
in a decolorized state.
BACKGROUND ART
[0002] There has hitherto been disclosed, as a photochromic
material having improved light fastness and coloration density, a
photochromic material comprising a photochromic compound selected
from a spirooxazine derivative or a spiropyran derivative, and a
styrene-based oligomer having a weight-average molecular weight of
200 to 6,000 (see, for example, Patent Document 1).
[0003] There is also disclosed, as a photochromic material which
has sufficient coloration density and can adjust the decolorization
sensitivity, a photochromic material comprising a photochromic
compound selected from a spirooxazine derivative or a spiropyran
derivative, and an acrylic oligomer having a weight-average
molecular weight of 12,000 or less (see, for example, Patent
Document 2).
[0004] There is also disclosed, as a photochromic composition which
can adjust the discoloration sensitivity, a photochromic
composition comprising a chromene-based photochromic compound
having a specific structure and a styrene-based or terpene-based
oligomer having a weight-average molecular weight of 250 to 4,000
(see, for example, Patent Document 3).
[0005] There is also disclosed, as a photochromic color material
which develops little residual color in a decolorized state and
high density in a colored state, a photochromic color material
comprising a photochromic compound and a terpenephenol resin (see,
for example, Patent Document 4).
[0006] The above-mentioned Patent Documents 1 to 4 disclose
inventions which can improve the light fastness and the coloration
density, and can be applied to various fields such as toy field,
writing instrument field, education field, medical field, interior
field, decoration field and printing field by adjusting the
discoloration sensitivity, but do not disclose application of a
naphthopyran-based photochromic compound having a specific
structure.
PRIOR ART DOCUMENT
Patent Document
[0007] Patent Document 1: JP 2005-48159 A
[0008] Patent Document 2: JP 2014-231573 A
[0009] Patent Document 3: JP 2010-180396 A
[0010] Patent Document 4: WO 2015/111744
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
[0011] According to the embodiments of the present invention, there
is provided a photochromic composition using a naphthopyran-based
photochromic compound having a specific structure and an oligomer,
which can adjust the discoloration sensitivity, and exhibits high
density in a colored state and little residual color in a
decolorized state.
Means for Solving the Problems
[0012] A requirement of the embodiments of the present invention is
a photochromic composition comprising a photochromic compound
represented by the following general formula (1) and an
oligomer:
##STR00001##
[0013] wherein, in the general formula (1), X.sup.1 and X.sup.2
represent an oxygen atom, Y.sup.1 and Y.sup.2 represent CH, R.sup.1
to R.sup.4 represent the general formula (2), R.sup.11 to R.sup.14
represent a hydrogen atom, a halogen atom, a hydroxyl group, a
nitrile group, an alkyl group, an aryl group, an alkoxy group, an
aryloxy group, an acyl group, an alkoxycarbonyl group or an
aryloxycarbonyl group, R.sup.15 represents an alkyl group having 3
or more carbon atoms, * represents a binding site to a pyran
skeleton, and X.sup.1 and Y.sup.1, and X.sup.2 and Y.sup.2 are each
bonded to adjacent carbon atoms of the carbon atoms constituting a
naphthalene skeleton.
[0014] Another requirements are that, in certain embodiments, the
general formula (1) is any one of the following general formulas
(3) to (9); in certain embodiments, the general formula (1) is any
one of the following general formulas (5) to (9); and in certain
embodiments, R.sup.15 is an alkyl group having 3 or more and 8 or
less carbon atoms.
##STR00002## ##STR00003##
[0015] Another requirements are that, in certain embodiments, the
oligomer is an oligomer selected from a styrene-based oligomer
having a weight-average molecular weight of 200 to 6,000, an
acrylic oligomer having a weight-average molecular weight of 12,000
or less, a terpene-based oligomer having a weight-average molecular
weight of 250 to 4,000 and a terpenephenol-based oligomer having a
weight-average molecular weight of 200 to 2,000; in certain
embodiments, a weight ratio of the photochromic compound to the
styrene-based oligomer or the acrylic oligomer is in the range of
1:1 to 1:10000; in certain embodiments, a weight ratio the
photochromic compound to the terpene-based oligomer is in the range
of 1:1 to 1:5000, in certain embodiments, a weight ratio of the
photochromic compound to the terpenephenol-based oligomer is in the
range of 1:1 to 1:50; and in certain embodiments, the photochromic
compound and the oligomer are encapsulated in microcapsules or
dispersed in resin particles.
[0016] Another requirements are that, in certain embodiments, the
photochromic composition comprises an ultraviolet absorber; and in
certain embodiments, the photochromic composition comprises an
ultraviolet absorber and a hindered amine-based light
stabilizer.
[0017] Still another requirements are that, in certain embodiments,
a photochromic liquid composition comprising the photochromic
composition and a vehicle; in certain embodiments, the photochromic
liquid composition is selected from printing inks, inks for writing
instruments, inks for applicators, inkjet inks, paints, ultraviolet
curable inks, drawing colors, cosmetics and fabric-coloring fluids;
in certain embodiments, a photochromic molding resin composition
comprising the photochromic composition and a molding resin; in
certain embodiments, a photochromic molded body obtained by molding
the photochromic molding resin composition; and in certain
embodiments, a photochromic laminated body comprising a support and
a photochromic layer containing the photochromic composition
provided on the support.
[0018] Still another requirements are that, in certain embodiments,
an article using the photochromic composition; and in certain
embodiments, the article is a toy, a packaging container, an
embroidery thread or an indicator.
Effects of the Invention
[0019] According to the embodiments of the present invention, there
is provided a photochromic composition using a naphthopyran-based
photochromic compound having a specific structure and an oligomer,
which can adjust the discoloration sensitivity, and exhibits high
density in a colored state and little residual color in a
decolorized state.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] FIG. 1 is a graph showing a relationship between the
wavelength and the absorbance of a photochromic compound.
MODE FOR CARRYING OUT THE INVENTION
[0021] Examples of the naphthopyran-based photochromic compound
represented by the general formula (1), which is applied to the
embodiments of the present invention, include: [0022]
2,2,7,7-tetra(4'-n-propoxyphenyl)-2H,7H-naphtho[1,2-b:4,3-b']-dipyran,
[0023]
2,2,7,7-tetra(4'-isopropoxyphenyl)-2H,7H-naphtho[1,2-b:4,3-b']-dip-
yran, [0024]
2,2,7,7-tetra(4'-n-butoxyphenyl)-2H,7H-naphtho[1,2-b:4,3-b']-dipyran,
[0025]
2,2,7,7-tetra(4'-isobutoxyphenyl)-2H,7H-naphtho[1,2-b:4,3-b']-dipy-
ran, [0026]
2,2,7,7-tetra(4'-sec-butoxyphenyl)-2H,7H-naphtho[1,2-b:4,3-b']-dipyran,
[0027]
2,2,7,7-tetra(4'-tert-butoxyphenyl)-2H,7H-naphtho[1,2-b:4,3-b']-di-
pyran, [0028]
2,2,7,7-tetra(4'-n-pentyloxyphenyl)-2H,7H-naphtho[1,2-b:4,3-b']-dipyran,
[0029]
2,2,7,7-tetra(4'-n-hexyloxyphenyl)-2H,7H-naphtho[1,2-b:4,3-b']-dip-
yran, [0030]
2,2,7,7-tetra(4'-n-heptyloxyphenyl)-2H,7H-naphtho[1,2-b:4,3-b']-dipyran,
[0031]
2,2,7,7-tetra(4'-n-octyloxyphenyl)-2H,7H-naphtho[1,2-b:4,3-b']-dip-
yran, [0032]
2,2,8,8-tetra(4'-n-propoxyphenyl)-2H,8H-naphtho[1,2-b:5,6-b']-dipyran,
[0033]
2,2,8,8-tetra(4'-isopropoxyphenyl)-2H,8H-naphtho[1,2-b:5,6-b']-dip-
yran, [0034]
2,2,8,8-tetra(4'-n-butoxyphenyl)-2H,8H-naphtho[1,2-b:5,6-b']-dipyran,
[0035]
2,2,8,8-tetra(4'-isobutoxyphenyl)-2H,8H-naphtho[1,2-b:5,6-b']-dipy-
ran, [0036]
2,2,8,8-tetra(4'-sec-butoxyphenyl)-2H,8H-naphtho[1,2-b:5,6-b']-dipyran,
[0037]
2,2,8,8-tetra(4'-tert-butoxyphenyl)-2H,8H-naphtho[1,2-b:5,6-b']-di-
pyran, [0038]
2,2,8,8-tetra(4'-n-pentyloxyphenyl)-2H,8H-naphtho[1,2-b:5,6-b']-dipyran,
[0039]
2,2,8,8-tetra(4'-n-hexyloxyphenyl)-2H,8H-naphtho[1,2-b:5,6-b']-dip-
yran, [0040]
2,2,8,8-tetra(4'-n-heptyloxyphenyl)-2H,8H-naphtho[1,2-b:5,6-b']-dipyran,
[0041]
2,2,8,8-tetra(4'-n-octyloxyphenyl)-2H,8H-naphtho[1,2-b:5,6-b']-dip-
yran, [0042]
3,3,8,8-tetra(4'-n-propoxyphenyl)-3H,8H-naphtho[2,1-b:5,6-b']-dipyran,
[0043]
3,3,8,8-tetra(4'-isopropoxyphenyl)-3H,8H-naphtho[2,1-b:5,6-b']-dip-
yran, [0044]
3,3,8,8-tetra(4'-n-butoxyphenyl)-3H,8H-naphtho[2,1-b:5,6-b']-dipyran,
[0045]
3,3,8,8-tetra(4'-isobutoxyphenyl)-3H,8H-naphtho[2,1-b:5,6-b']-dipy-
ran, [0046]
3,3,8,8-tetra(4'-sec-butoxyphenyl)-3H,8H-naphtho[2,1-b:5,6-b']-dipyran,
[0047]
3,3,8,8-tetra(4'-tert-butoxyphenyl)-3H,8H-naphtho[2,1-b:5,6-b']-di-
pyran, [0048]
3,3,8,8-tetra(4'-n-pentyloxyphenyl)-3H,8H-naphtho[2,1-b:5,6-b']-dipyran,
[0049]
3,3,8,8-tetra(4'-n-hexyloxyphenyl)-3H,8H-naphtho[2,1-b:5,6-b']-dip-
yran, [0050]
3,3,8,8-tetra(4'-n-heptyloxyphenyl)-3H,8H-naphtho[2,1-b:5,6-b']-dipyran,
[0051]
3,3,8,8-tetra(4'-n-octyloxyphenyl)-3H,8H-naphtho[2,1-b:5,6-b']-dip-
yran, [0052]
2,2,10,10-tetra(4'-n-propoxyphenyl)-2H,10H-naphtho[1,2-b:7,8-b']-dipyran,
[0053]
2,2,10,10-tetra(4'-isopropoxyphenyl)-2H,10H-naphtho[1,2-b:7,8-b']--
dipyran, [0054]
2,2,10,10-tetra(4'-n-butoxyphenyl)-2H,10H-naphtho[1,2-b:7,8-b']-dipyran,
[0055]
2,2,10,10-tetra(4'-isobutoxyphenyl)-2H,10H-naphtho[1,2-b:7,8-b']-d-
ipyran, [0056]
2,2,10,10-tetra(4'-sec-butoxyphenyl)-2H,10H-naphtho[1,2-b:7,8-b']-dipyran-
, [0057]
2,2,10,10-tetra(4'-tert-butoxyphenyl)-2H,10H-naphtho[1,2-b:7,8-b'-
]-dipyran, [0058]
2,2,10,10-tetra(4'-n-pentyloxyphenyl)-2H,10H-naphtho[1,2-b:7,8-b']-dipyra-
n, [0059]
2,2,10,10-tetra(4'-n-hexyloxyphenyl)-2H,10H-naphtho[1,2-b:7,8-b'-
]-dipyran, [0060]
2,2,10,10-tetra(4'-n-heptyloxyphenyl)-2H,10H-naphtho[1,2-b:7,8-b']-dipyra-
n, [0061]
2,2,10,10-tetra(4'-n-octyloxyphenyl)-2H,10H-naphtho[1,2-b:7,8-b'-
]-dipyran, [0062]
3,3,6,6-tetra(4'-n-propoxyphenyl)-3H,6H-naphtho[2,1-b:3,4-b']-dipyran,
[0063]
3,3,6,6-tetra(4'-isopropoxyphenyl)-3H,6H-naphtho[2,1-b:3,4-b']-dip-
yran, [0064]
3,3,6,6-tetra(4'-n-butoxyphenyl)-3H,6H-naphtho[2,1-b:3,4-b']-dipyran,
[0065]
3,3,6,6-tetra(4'-isobutoxyphenyl)-3H,6H-naphtho[2,1-b:3,4-b']-dipy-
ran, [0066]
3,3,6,6-tetra(4'-sec-butoxyphenyl)-3H,6H-naphtho[2,1-b:3,4-b']-dipyran,
[0067]
3,3,6,6-tetra(4'-tert-butoxyphenyl)-3H,6H-naphtho[2,1-b:3,4-b']-di-
pyran, [0068]
3,3,6,6-tetra(4'-n-pentyloxyphenyl)-3H,6H-naphtho[2,1-b:3,4-b']-dipyran,
[0069]
3,3,6,6-tetra(4'-n-hexyloxyphenyl)-3H,6H-naphtho[2,1-b:3,4-b']-dip-
yran, [0070]
3,3,6,6-tetra(4'-n-heptyloxyphenyl)-3H,6H-naphtho[2,1-b:3,4-b']-dipyran,
[0071]
3,3,6,6-tetra(4'-n-octyloxyphenyl)-3H,6H-naphtho[2,1-b:3,4-b']-dip-
yran, [0072]
3,3,9,9-tetra(4'-n-propoxyphenyl)-3H,9H-naphtho[2,1-b:6,5-b']-dipyran,
[0073]
3,3,9,9-tetra(4'-isopropoxyphenyl)-3H,9H-naphtho[2,1-b:6,5-b']-dip-
yran, [0074]
3,3,9,9-tetra(4'-n-butoxyphenyl)-3H,9H-naphtho[2,1-b:6,5-b']-dipyran,
[0075]
3,3,9,9-tetra(4'-isobutoxyphenyl)-3H,9H-naphtho[2,1-b:6,5-b']-dipy-
ran, [0076]
3,3,9,9-tetra(4'-sec-butoxyphenyl)-3H,9H-naphtho[2,1-b:6,5-b']-dipyran,
[0077]
3,3,9,9-tetra(4'-tert-butoxyphenyl)-3H,9H-naphtho[2,1-b:6,5-b']-di-
pyran, [0078]
3,3,9,9-tetra(4'-n-pentyloxyphenyl)-3H,9H-naphtho[2,1-b:6,5-b']-dipyran,
[0079]
3,3,9,9-tetra(4'-n-hexyloxyphenyl)-3H,9H-naphtho[2,1-b:6,5-b']-dip-
yran, [0080]
3,3,9,9-tetra(4'-n-heptyloxyphenyl)-3H,9H-naphtho[2,1-b:6,5-b']-dipyran,
[0081]
3,3,9,9-tetra(4'-n-octyloxyphenyl)-3H,9H-naphtho[2,1-b:6,5-b']-dip-
yran, [0082]
3,3,10,10-tetra(4'-n-propoxyphenyl)-3H,10H-naphtho[2,1-b:7,8-b']-dipyran,
[0083]
3,3,10,10-tetra(4'-isopropoxyphenyl)-3H,10H-naphtho[2,1-b:7,8-b']--
dipyran, [0084]
3,3,10,10-tetra(4'-n-butoxyphenyl)-3H,10H-naphtho[2,1-b:7,8-b']-dipyran,
[0085]
3,3,10,10-tetra(4'-isobutoxyphenyl)-3H,10H-naphtho[2,1-b:7,8-b']-d-
ipyran, [0086]
3,3,10,10-tetra(4'-sec-butoxyphenyl)-3H,10H-naphtho[2,1-b:7,8-b']-dipyran-
, [0087]
3,3,10,10-tetra(4'-tert-butoxyphenyl)-3H,10H-naphtho[2,1-b:7,8-b'-
]-dipyran, [0088]
3,3,10,10-tetra(4'-n-pentyloxyphenyl)-3H,10H-naphtho[2,1-b:7,8-b']-dipyra-
n, [0089]
3,3,10,10-tetra(4'-n-hexyloxyphenyl)-3H,10H-naphtho[2,1-b:7,8-b'-
]-dipyran, [0090]
3,3,10,10-tetra(4'-n-heptyloxyphenyl)-3H,10H-naphtho[2,1-b:7,8-b']-dipyra-
n, [0091]
3,3,10,10-tetra(4'-n-octyloxyphenyl)-3H,10H-naphtho[2,1-b:7,8-b'-
]-dipyran, and the like.
[0092] The naphthopyrane-based photochromic compound applied to the
embodiments of the present invention develops an orange to red
color at the time of coloration due to having an alkoxy group.
[0093] R.sup.15 in the general formula (2) of the
naphthopyran-based photochromic compound is an alkyl group having 3
or more carbon atoms, preferably an alkyl group having 3 or more
and 8 or less carbon atoms, more preferably an alkyl group having 3
or 4 carbon atoms, such as a propyl group, an isopropyl group, an
n-butyl group, an isobutyl group, a sec-butyl group or a tert-butyl
group, and still more preferably a sec-butyl group.
[0094] When the number of carbon atoms of the alkyl group of
R.sup.15 in the general formula (2) satisfies the above range, the
naphthopyran-based photochromic compound exhibits excellent
solubility in the oligomer, thus making it easier to exhibit high
density in a colored state.
[0095] The naphthopyran-based photochromic compound can develop a
color by sunlight, and can also undergo discoloration using a light
irradiator equipped with a light source for irradiating light.
[0096] The light source preferably has a peak emission wavelength
in the range of 400 to 495 nm and suitably irradiates blue light.
Unlike a light irradiator that irradiates ultraviolet light having
a peak emission wavelength in the vicinity of 350 to 390 nm, which
is a light source that satisfactorily causes discoloration of a
conventional photochromic compound, the light source irradiates
violet to blue light, thus having little effect on the human body,
leading to high safety.
[0097] It is possible to use, as the light source, any light source
having the above-mentioned peak emission wavelength, and a blue
light emitting diode is preferably used.
[0098] Examples of the light emitting diode include blue LED
manufactured by Nichia Corporation under the trade name of
NSPB336CS (peak wavelength of 465 nm); blue LED manufactured by
Kyosemi Corporation under the trade name of KED471M53A (peak
wavelength of 465 nm); blue LED manufactured by SEIWA ELECTRIC MFG.
CO., LTD. under the trade name of SDDB16001A1 (peak wavelength of
460 nm); purple LED manufactured by Kyosemi Corporation under the
trade name of KED405UH3 (peak wavelength of 405 nm); purple LED
manufactured by OPTOSUPPLY, under the trade name of OSSV5111A (peak
wavelength of 430 nm); purple LED manufactured by OPTOSUPPLY under
the trade name of OSSV9131A (peak wavelength of 430 nm), and the
like.
[0099] Regarding the naphthopyran-based photochromic compound, the
integrated value of absorbance (x) in the wavelength range from the
wavelength showing a maximum absorbance of less than 400 nm to the
wavelength of 400 nm and the integrated value of absorbance (y) in
a wavelength range of 400 nm to 700 nm satisfy the following
expression (1) (see FIG. 1).
y/x.gtoreq.0.02 (1)
By satisfying the expression (1), the naphthopyran-based
photochromic compound exhibits photochromic properties for a light
source having a peak wavelength in the range of from 400 to 495 nm
and can give a viewable color density upon light irradiation.
[0100] If the value of y/x is less than 0.02, even when irradiated
with light using a light irradiator, the photochromic compound does
not develop a color or hardly develops a color, thus failing to
obtain a sufficient color density, so that it is difficult for the
user to visually recognize the color change.
[0101] The value of y/x is preferably 0.025 or more, and more
preferably 0.03 or more.
[0102] The naphthopyran-based photochromic compound is used by
dissolving in an oligomer. Examples of the oligomer include
styrene-based oligomers, acrylic oligomers, terpene-based
oligomers, terpene-based oligomers, and the like.
[0103] The styrene-based oligomer to be used has a weight-average
molecular weight of 200 to 6,000, and preferably 200 to 4,000.
[0104] If the weight-average molecular weight of the styrene-based
oligomer exceeds 6,000, a residual color occurs by light
irradiation and the coloration density easily decreases. Since it
becomes difficult to adjust the discoloration sensitivity, it is
desirable that the weight-average molecular weight is within the
above range.
[0105] Meanwhile, if the weight-average molecular weight is less
than 200, the content of the monomer increases, leading to a lack
of stability, and thus the light fastness easily deteriorates.
[0106] The styrene-based oligomer is a compound having a styrene
skeleton, or a hydrogenated product thereof, and specific examples
thereof include a low molecular weight polystyrene, a
styrene-.alpha.-methylstyrene copolymer, an .alpha.-methylstyrene
polymer, a copolymer of .alpha.-methylstyrene and vinyltoluene, and
the like.
[0107] Examples of the low molecular weight polystyrene include
those manufactured by Sanyo Chemical Industries, Ltd. under the
trade names of Hymer SB-75 (weight-average molecular weight of
2,000), Hymer ST-95 (weight-average molecular weight of 4,000), and
the like.
[0108] Examples of the styrene-.alpha.-methylstyrene copolymer
include those manufactured by Eastman Chemical Company under the
trade names of Picolastic A-5 (weight-average molecular weight of
317), Picolastic A-75 (weight-average molecular weight of 917), and
the like.
[0109] Examples of the .alpha.-methylstyrene polymer include those
manufactured by Eastman Chemical Company under the trade names of
Kristalex 3085 (weight-average molecular weight of 664), Kristalex
3100 (weight-average molecular weight of 1,020), Kristalex 1120
(weight-average molecular weight of 2,420), and the like.
[0110] Examples of the copolymer of .alpha.-methylstyrene and
vinyltoluene include those manufactured by Eastman Chemical Company
under the trade names of Piccotex LC (weight-average molecular
weight of 950), Piccotex 100 (weight-average molecular weight of
1,740), and the like.
[0111] The acrylic oligomer to be used has a weight-average
molecular weight of 12,000 or less, preferably 1,000 to 8,000, and
more preferably 1,500 to 6,000.
[0112] If the weight-average molecular weight of the acrylic
oligomer exceeds 12,000, it becomes difficult to adjust the
discoloration sensitivity, so that it is desirable that the
weight-average molecular weight is within the above range.
[0113] Meanwhile, if the weight-average molecular weight is less
than 1,000, the content of the monomer increases, leading to a lack
of stability, and thus the coloration density easily decreases and
the light fastness easily deteriorates.
[0114] Specific examples of the acrylic oligomer include an acrylic
acid ester copolymer, and the like.
[0115] Examples of the acrylic acid ester copolymer include those
manufactured by TOAGOSEI CO., LTD. under the trade names of ARUFON
UP-1170 (weight-average molecular weight of 8,000), ARUFON UP-1080
(weight-average molecular weight of 6,000), ARUFON UP-1000
(weight-average molecular weight of 3,000), ARUFON UP-1020
(weight-average molecular weight of 2,000), ARUFON UP-1010
(weight-average molecular weight of 1,700), ARUFON UH-2,000
(weight-average molecular weight of 11,000), ARUFON US-6100
(weight-average molecular weight of 2,500), ARUFON UC-3510
(weight-average molecular weight of 2,000), and the like.
[0116] The terpene-based oligomer to be used has a weight-average
molecular weight of 250 to 4,000, and preferably 300 to 4,000.
[0117] If the weight-average molecular weight of the terpene-based
oligomer exceeds 4,000, a residual color occurs by light
irradiation and the coloration density easily decreases. In
addition, it becomes difficult to adjust the discoloration
sensitivity. Thus it is desirable that the weight-average molecular
weight is within the above range.
[0118] Meanwhile, if the weight-average molecular weight is less
than 250, the content of the monomer increases, leading to a lack
of stability, and thus the light fastness easily deteriorates.
[0119] The terpene-based oligomer is a compound having a terpene
skeleton, and specific examples thereof include an .alpha.-pinene
polymer, a .beta.-pinene polymer, a d-limonene polymer, and the
like.
[0120] Examples of the .alpha.-pinene polymer include those
manufactured by Eastman Chemical Company under the trade name of
Piccolite A115 (weight-average molecular weight of 833), and the
like.
[0121] Examples of the .beta.-pinene polymer include those
manufactured by Eastman Chemical Company under the trade name of
Piccolite 5115 (weight-average molecular weight of 1,710), and the
like.
[0122] Examples of the d-limonene polymer include those
manufactured by Eastman Chemical Company, under the trade name of
Piccolite C115 (weight-average molecular weight of 902), and the
like
[0123] The terpenephenol-based oligomer to be used has a
weight-average molecular weight of 200 to 2,000, and preferably 500
to 1,200.
[0124] If the weight-average molecular weight of the
terpenephenol-based oligomer exceeds 2,000, it becomes difficult to
adjust the discoloration sensitivity, so that it is desirable that
the weight-average molecular weight is within the above range.
[0125] Meanwhile, if the weight-average molecular weight is less
than 200, the content of the monomer increases, leading to a lack
of stability, and thus the light fastness easily deteriorates.
[0126] The terpenephenol-based oligomer is a compound obtained by
copolymerizing a cyclic terpene monomer with phenols, or a
hydrogenated product thereof, and specific examples thereof include
an .alpha.-pinene-phenol copolymer, and the like.
[0127] Examples of the .alpha.-pinene-phenol copolymer include
those manufactured by YASUHARA CHEMICAL CO., LTD. under the trade
names of YS POLYSTAR T145 (weight-average molecular weight of
1,050), YS POLYSTAR T130 (weight-average molecular weight of 900),
YS POLYSTAR T500 (weight-average molecular weight of 500), YS
POLYSTAR 5145 (weight-average molecular weight of 1,050), and the
like.
[0128] The weight-average molecular weight of the styrene-based
oligomer, acrylic oligomer, terpene-based oligomer or
terpenephenol-based oligomer is measured by the GPC method (gel
permeation chromatography).
[0129] The oligomer may be used alone or in combination of two or
more thereof.
[0130] The weight ratio of the photochromic compound to the
styrene-based oligomer or the acrylic oligomer is preferably 1:1 to
1:10000, and more preferably 1:5 to 1:500.
[0131] The weight ratio of the photochromic compound to the
terpene-based oligomer is preferably 1:1 to 1:5000, and more
preferably 1:5 to 1:500.
[0132] The weight ratio of the photochromic compound to the
terpenephenol-based oligomer is preferably 1:1 to 1:50, more
preferably 1:2 to 1:30, and still more preferably 1:2 to 1:20.
[0133] When the weight ratio of the photochromic compound to the
oligomer satisfies the above range, the photochromic compound
satisfies the coloration/decolorization function and easily exhibit
sufficient coloration density.
[0134] It is also possible to improve the light fastness by adding
an ultraviolet absorber to the photochromic composition according
to the embodiments of the present invention.
[0135] Ultraviolet absorbers are illustrated below, but the
embodiments of the present invention are not limited to these
compounds: [0136] benzophenone-based ultraviolet absorbers such as
2,4-dihydroxybenzophenone, [0137] 2-hydroxy-4-methoxybenzophenone,
[0138] 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, [0139]
2,2',4,4'-tetrahydroxybenzophenone, [0140]
2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, [0141]
2-hydroxy-4-octyloxybenzophenone, [0142]
bis-(2-methoxy-4-hydroxy-5-benzoylphenyl)methane, [0143]
2-(2'-hydroxy-3',5'-di-t-amylphenyl)-benzophenone, [0144]
2-hydroxy-4-dodecyloxybenzophenone, [0145]
2-hydroxy-4-octadecyloxybenzophenone, [0146]
2,2'-dihydroxy-4-methoxybenzophenone, and [0147]
2-hydroxy-4-benzyloxybenzophenone; [0148] salicylic acid-based
ultraviolet absorbers such as phenyl salicylate, [0149]
para-t-butylphenyl salicylate, [0150] paraoctylphenyl salicylate,
[0151] 2,4-di-t-butylphenyl-4-hydroxybenzoate, [0152]
1-hydroxybenzoate, [0153] 1-hydroxy-3-t-butylbenzoate, [0154]
1-hydroxy-3-t-octylbenzoate, and [0155] resorcinol monobenzoate;
[0156] cyanoacrylate-based ultraviolet absorbers such as
ethyl-2-cyano-3,3'-diphenylacrylate, [0157]
2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, and [0158]
2-ethylhexyl-2-cyano-3-phenyl cinnate; [0159] benzotriazole-based
ultraviolet absorbers such as
2-(5-t-butyl-2-hydroxyphenyl)-benzotriazole, [0160]
2-(5-methyl-2-hydroxyphenyl)-benzotriazole, [0161]
2-[2-hydroxy-3,5-bis(a,a-dimethylbenzyl)phenyl]-2H-benzotriazole,
[0162] 2-(3,5-di-t-butyl-2-hydroxyphenyl)-benzotriazole, [0163]
2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole,
[0164] 2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole,
[0165] 2-(3,5-di-t-amyl-2-hydroxyphenyl)-benzotriazole, [0166]
2-(3-dodecyl-5-methyl-2-hydroxyphenyl)benzotriazole, [0167]
2-(3-t-butyl-5-propyloctylate-2-hydroxyphenyl)-5-chlorobenzotriazole,
[0168] 2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole, [0169]
2-(3-t-butyl-5-octyloxycarbonylethyl-2-hydroxyphenyl)-benzotriazole,
[0170] 2-(2-hydroxy-4-octyloxyphenyl)-benzotriazole, [0171]
2-[2-hydroxy-3-dimethylbenzylphenyl-5-(1,1,3,3-tetramethylbutyl)]-2H-benz-
otriazole, and [0172]
2-[2'-hydroxy-3'-(3'',4'',5'',6''-tetrahydrophthalimidemethyl)-5'-methylp-
henyl]-benzotriazole; [0173] oxalic anilide-based ultraviolet
absorbers such as
ethanediamide-N-(2-ethoxyphenyl)-N'-(4-isododecylphenyl), and
[0174]
2,2,4,4-tetramethyl-20-(.beta.-lauryl-oxycarbonyl)-ethyl-7-oxa-3,2-
0-diazodispiro(5,1,11,2)heneicosan-21-one; [0175] triazine-based
ultraviolet absorbers such as
2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, [0176]
2,4-diphenyl-6-(2-hydroxy-4-ethoxyphenyl)-1,3,5-triazine, [0177]
2,4-diphenyl-6-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, [0178]
2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, [0179]
2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, [0180]
2,4-diphenyl-6-(2-hydroxy-4-pentyloxyphenyl)-1,3,5-triazine, [0181]
2,4-diphenyl-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, [0182]
2,4-diphenyl-6-(2-hydroxy-4-dodecyloxyphenyl)-1,3,5-triazine,
[0183] 2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine,
[0184]
2,4-diphenyl-6-[2-hydroxy-4-(2-butoxyethoxy)phenyl]-1,3,5-triazine,
[0185] 2,4-di-p-tolyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine,
[0186] 2,4-di-p-tolyl-6-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine,
[0187] 2,4-di-p-tolyl-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine,
[0188]
2,4-di-p-tolyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine,
[0189]
2,4-di-p-tolyl-6-(2-hydroxy-4-pentyloxyphenyl)-1,3,5-triazine,
[0190]
2,4-di-p-tolyl-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,
[0191]
2,4-di-p-tolyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine,
[0192]
2,4-di-p-tolyl-6-[2-hydroxy-4-(2-hexyloxyethoxy)phenyl]-1,3,5-triazine,
[0193]
2-{4-[2-hydroxy-3-(dodecyloxy)propyloxy]-2-hydroxyphenyl}-4,6-bis(-
2,4-dimethylphenyl)-1,3,5-triazine, [0194]
2-{4-[2-hydroxy-3-(tridecyloxy)propyloxy]-2-hydroxyphenyl}-4,6-bis(2,4-di-
methylphenyl)-1,3,5-triazine, [0195]
2-{4-[2-hydroxy-3-(2'-ethyl)hexyloxy]-2-hydroxyphenyl}-4,6-bis(2,4-dimeth-
ylphenyl)-1,3,5-triazine, [0196] a mixture of
2-{4-[2-hydroxy-3-(tridecyloxy)propyloxy]-2-hydroxyphenyl}-4,6-bis(2,4-di-
methylphenyl)-1,3,5-triazine and
2-{4-[2-hydroxy-3-(dodecyloxy)propyloxy]-2-hydroxyphenyl}-4,6-bis(2,4-dim-
ethylphenyl)-1,3,5-triazine, [0197]
2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-bis-butoxyphenyl)-1,3,5-triazine-
, [0198]
2-{2-hydroxy-4-[(1-octyloxycarbonylethoxy)phenyl]}-4,6-bis(4-phen-
ylphenyl)-1,3,5-triazine [0199]
2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine-
, [0200]
2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-
e, [0201] 2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1,3,5-triazine,
[0202] 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,
and [0203] tris(3-methylanilino)triazine; and the like.
[0204] It is also possible to further improve the light fastness by
adding an ultraviolet absorber and a hindered amine-based light
stabilizer in combination to the photochromic composition according
to the embodiments of the present invention.
[0205] Hindered amine-based light stabilizers are illustrated
below, but the embodiments of the present invention are not limited
to these compounds: [0206] bis(1,2,2,6,6-pentamethyl-4-piperidyl)
sebacate, [0207]
2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonic acid
bis(1,2,2,6,6-pentamethyl-4-piperidyl), [0208]
butane-1,2,3,4-tetracarboxylic acid
tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl), [0209]
butane-1,2,3,4-tetracarboxylic acid
tetrakis(2,2,6,6-tetramethyl-4-piperidyl), [0210]
bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, [0211]
bis[2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidyl] sebacate, [0212]
a mixed esterified product of butane-1,2,3,4-tetracarboxylic acid
with 1,2,2,6,6-pentamethyl-4-piperidinol and
3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane,
[0213] bis(1-octyloxy-2,2,6,6-tetramethyl) sebacate, [0214] a mixed
esterified product of butane-1,2,3,4-tetracarboxylic acid with
2,2,6,6-tetramethyl-4-piperidinol and
3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane,
[0215] a mixed esterified product of butane-1,2,3,4-tetracarboxylic
acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol,
[0216] 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, [0217] a
mixture of bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate with
1-methyl-10-(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, [0218]
N,N',N'',N'''-tetrakis-{4,6-bis-[butyl-(N-methyl-2,2,6,6-tetramethylpiper-
idin-4-yl)amino]-triazin-2-yl}-4,7-diazadecane-1,10-diamine, [0219]
N-methyl-3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidinyl)pyrrolidine-2,5-d-
ione, and the like.
[0220] As the hindered amine-based light stabilizer, a compound
represented by the following general formula (10) is suitably
used:
##STR00004##
wherein R.sub.1 represents an alkyl group having 1 to 30 carbon
atoms, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 each represent an
alkyl group having 1 to 5 carbon atoms, n represents an integer of
1 or more, and R.sub.6 represents an n-valent organic residue.
[0221] In the photochromic composition according to the embodiments
of the present invention, a combination of an ultraviolet absorber
and a hindered amine-based light stabilizer for the purpose of
obtaining excellent light fastness is preferably a combination of
an ultraviolet absorber selected from a benzotriazole-based
ultraviolet absorber or a triazine-based ultraviolet absorber, and
a hindered amine-based light stabilizer; and more preferably a
combination of an ultraviolet absorber selected from
2-(2-hydroxy-5-t-butylphenyl)-benzotriazole,
2-[2-hydroxy-3-dimethylbenzylphenyl-5-(1,1,3,3-tetramethylbutyl)]-2H-benz-
otriazole, 2-(2-hydroxy-5-methylphenyl)-benzotriazole, or a mixture
of
2-{4-[2-hydroxy-3-(tridecyloxy)propyloxy]-2-hydroxyphenyl}-4,6-bis(2,4-di-
methylphenyl)-1,3,5-triazine and
2-{4-[2-hydroxy-3-(dodecyloxy)propyloxy]-2-hydroxyphenyl}-4,6-bis(2,4-dim-
ethylphenyl)-1,3,5-triazine, and a hindered amine-based light
stabilizer selected from
2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonic acid
bis(1,2,2,6,6-pentamethyl-4-piperidyl),
bis[2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidyl] sebacate, or a
mixture of bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and
1-methyl 10-(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate.
[0222] The photochromic composition according to the embodiments of
the present invention may be encapsulated in microcapsules to form
a photochromic microcapsule pigment, or dispersed in a
thermoplastic or thermosetting resin to form photochromic resin
particles.
[0223] The photochromic composition can be encapsulated in
microcapsules to form a chemically and physically stable pigment.
There have conventionally been well-known, as the method of the
microencapsulation, an interfacial polymerization method of an
isocyanate-based compound, an in-situ polymerization method of a
melamine-formalin-based composition, a liquid-phase curing coating
method, a phase separation method from an aqueous solution, a phase
separation method from an organic solvent, a melt dispersion
cooling method, a gas-phase suspension coating method, a spray
drying method, and the like. Any of them is appropriately selected
depending on use application. On the surface of the microcapsules,
another secondary resinous coating may be provided for practical
use depending on the use purpose in order to impart the durability
or modify the surface properties.
[0224] The photochromic microcapsule pigment preferably has a mass
ratio of inclusions:wall film of 7:1 to 1:1. If the mass ratio of
inclusions to wall film is in the above range, it is possible to
prevent deterioration of the color density and the sharpness at the
time of coloration. The mass ratio of inclusions:wall film is more
preferably 6:1 to 1:1.
[0225] The photochromic microcapsule pigment or resin particles
fulfill practical applicability if the average particle size is in
the range of 0.5 to 100 .mu.m, preferably 1 to 50 .mu.m, and more
preferably 1 to 30 .mu.m.
[0226] The photochromic microcapsule pigment or resin particles
lack in dispersion stability and processing suitability for the
operation of blending into ink, paint or resin, if the average
particle size thereof exceeds 100 .mu.m. Meanwhile, if the average
particle size thereof is less than 0.5 .mu.m, it becomes difficult
to exhibit high-density coloration.
[0227] In the measurement of the average particle size, the region
of particles is determined using an image analysis type particle
size distribution measuring software "Mac-View" manufactured by
Mountech Co., Ltd., a projected area equivalent circle diameter
(Heywood diameter) is calculated from the area of the region of
particles, and the average particle size is measured as an average
particle size of particles equivalent to an equal volume sphere
based on the calculated value.
[0228] When the particle diameter of all particles or most of the
particles exceed 0.2 .mu.m, the average particle size can also be
measured as an average particle size of particles equivalent to an
equal volume sphere by the Coulter method using a particle size
distribution analyzer (manufactured by Beckman-Coulter, Inc. under
the product name of Multisizer 4e).
[0229] A volumetric particle size and an average particle size may
be measured using a calibrated laser diffraction/scattering
particle size distribution analyzer (LA-300, manufactured by
Horiba, Ltd.) based on the numerical value measured by the above
software or the Coulter method using a measurement device.
[0230] The photochromic composition, the microcapsule pigment or
resin particles can be used for photochromic liquid compositions
such as, for example, printing inks for screen printing, offset
printing, process printing, gravure printing, coater printing and
tampo printing: paints for brush coating, spray coating,
electrostatic coating, electro-deposition coating, flow coating,
roller coating and immersion coating; inks for inkjet recording;
ultraviolet curable inks; inks for writing instruments or
applicators such as those for marking pens, ballpoint pens,
fountain pens and brush-type pens; drawing colors, cosmetics and
fabric-coloring fluids; by being dispersed in a vehicle containing
water and/or an organic solvent, and various additives as
necessary.
[0231] Various additives can be added to the photochromic liquid
composition, and examples thereof include resins, crosslinking
agents, curing agents, desiccants, plasticizers, viscosity
adjusters, dispersants, UV absorbers, antioxidants, light
stabilizers, antisetting agents, smoothing agents, gelling agents,
defoamers, delustrant agents, penetrating agents, pH adjusters,
foaming agents, coupling agents, moisturizers, fungicides,
preservatives, rust preventives, and the like.
[0232] Of these, examples of the vehicle for writing instruments
used for inks for writing instruments ink include an oil-based
vehicle containing an organic solvent, or an aqueous vehicle
containing water, and an organic solvent as necessary.
[0233] Examples of the organic solvent include ethanol, propanol,
butanol, glycerin, sorbitol, triethanolamine, diethanolamine,
monoethanolamine, ethylene glycol, diethylene glycol,
thiodiethylene glycol, polyethylene glycol, propylene glycol,
butylene glycol, ethylene glycol monomethyl ether, ethylene glycol
monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol
monomethyl ether, diethylene glycol monoethyl ether, diethylene
glycol monobutyl ether, propylene glycol monobutyl ether, ethylene
glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone,
N-methyl-2-pyrrolidone, and the like.
[0234] Examples of the ink for writing instruments include
shear-thinning inks containing a shear-thinning agent in a vehicle,
and cohesive inks containing a water-soluble polymer flocculant in
a vehicle and a pigment suspended in a loosely agglomerated
state.
[0235] By adding the shear-thinning agent, it is possible to
suppress the aggregation and sedimentation of the pigment and also
to suppress the bleeding of the handwriting, thus making it
possible to form satisfactory handwriting.
[0236] Furthermore, when the writing instrument filled with the
above ink is in the form of a ballpoint pen, it is possible to
prevent ink from leaking from the gap between the ball and the tip
when not in use, or it is possible to prevent backflow when the
writing tip is left facing upward (upright state).
[0237] Examples of the shear-thinning agent include xanthan gum,
welan gum, succinoglycan (average molecular weight of about 1 to 8
million), which is an organic acid-modified heteropolysaccharide
whose constituent monosaccharides are glucose and galactose, guar
gum, locust bean gum and derivatives thereof, hydroxyethyl
cellulose, alginic acid alkyl esters, polymers having a molecular
weight of 100,000 to 150,000 containing alkyl esters of methacrylic
acid as main components, thickening polysaccharides having gelling
ability extracted from seaweeds such as glucomannan, agar and
caragenin, benzylene sorbitol and benzylene xylitol or derivatives
thereof, crosslinkable acrylic acid polymers, inorganic fine
particles, polyglycerin fatty acid esters, polyoxyethylene sorbitan
fatty acid esters, polyethylene glycol fatty acid esters,
polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers,
polyoxyethylene alkyl phenyl ethers, nonionic surfactants having an
HLB value of 8 to 12 such as fatty acid amides, salts of dialkyl or
dialkenyl sulfosuccinic acid, mixtures of N-alkyl-2-pyrrolidone and
anionic surfactants, mixtures of polyvinyl alcohol and an acrylic
resin, and the like.
[0238] Examples of the water-soluble polymer flocculant include
polyvinylpyrrolidone, polyethylene oxide, water-soluble
polysaccharides, and the like.
[0239] Examples of the water-soluble polysaccharides include
traganth gum, guar gum, pullulan, cyclodextrin, water-soluble
cellulose derivatives, and the like. Specific examples of the
water-soluble cellulose derivatives include methyl cellulose,
hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl
methyl cellulose, hydroxypropyl methyl cellulose, and the like.
[0240] By using a comb-shaped polymer dispersant having a carboxyl
group in the side chain and an organic nitrogen sulfur compound
together with the polymer flocculant, it is possible to improve the
dispersibility of loose aggregates of the microcapsule pigment by
the polymer flocculant.
[0241] The comb-shaped polymer dispersant having a carboxyl group
in the side chain is not particularly limited as long as it is a
comb-shaped polymer compound having a plurality of carboxyl groups
in the side chain, and an acrylic polymer compound having a
plurality of carboxyl groups in the side chain is suitable, and
specific examples thereof include those manufactured by Lubrizol
Japan Limited under the trade name of Solspers 43000.
[0242] The organic nitrogen-sulfur compound further suppresses the
sedimentation of the microcapsule pigment due to vibration when the
writing instrument is filled with ink and put into practical
use.
[0243] This further improves the dispersibility in which the loose
aggregates of the microcapsule pigment are dispersed by the
comb-shaped polymer dispersant having a carboxyl group in the side
chain.
[0244] As the organic nitrogen sulfur compound, a compound selected
from thiazole-based compounds, isothiazole-based compounds,
benzothiazole-based compounds and benzoisothiazole-based compounds
is used.
[0245] Specifically, one or more compounds selected from
2-(4-thiazoyl)-benzimidazole (TBZ),
2-(thiocyanatomethylthio)-1,3-benzothiazole (TCMTB),
2-methyl-4-isothiazolin-3-one and
5-chloro-2-methyl-4-isothiazolin-3-one are used as the organic
nitrogen-sulfur compound, and one or more compounds selected from
2-(4-thiazoyl)-benzimidazole (TBZ), 2-methyl-4-isothiazolin-3-one
and 5-chloro-2-methyl-4-isothiazolin-3-one are preferably used.
[0246] Examples of the organic nitrogen sulfur compound include
those manufactured by Permachem Asia Ltd. under the trade names of
Top Side 88, Top Side 133, Top Side 170, Top Side 220, Top Side
288, Top Side 300, Top Side 400, Top Side 500, Top Side 600, Top
Side 700Z, Top Side 800 and Top Side 950; and those manufactured by
HOKKO SANGYO Co., LTD. under the trade names of HOKUSTAR HP,
HOKUSTAR E50A, HOKUSIDE P200, HOKUSIDE 6500, HOKUSIDE 7400,
HOKUSIDE MC, HOKUSIDE 369 and HOKUSIDE R-150.
[0247] The mass ratio of the comb-shaped polymer dispersant having
a carboxyl group in the side chain to the organic nitrogen sulfur
compound is 1:1 to 1:10, and preferably 1:1 to 1:5. By satisfying
the above range, it is possible to sufficiently achieve the
dispersibility of loose aggregates of the microcapsule pigment and
the suppression of sedimentation of the microcapsule pigment due to
vibration.
[0248] The addition of a water-soluble resin applied for imparting
the fixability to the paper surface of handwriting and viscosity
further improves the function of enhancing the stability of the
microcapsule pigment in the ink containing the above-mentioned
comb-shaped polymer dispersant having a carboxyl group in the side
chain and organic nitrogen sulfur compound mentioned above.
[0249] Examples of the water-soluble resin include an alkyd resin,
an acrylic resin, a styrene-maleic acid copolymer, cellulose
derivatives, polyvinylpyrrolidone, polyvinyl alcohol, dextrin, and
the like, and polyvinyl alcohol is preferably used.
[0250] A partially saponified polyvinyl alcohol having a
saponification degree of 70 to 89 mol % is more suitably used as
the polyvinyl alcohol since the ink is highly soluble even in an
acidic region.
[0251] The water-soluble resin is added in the ink in the amount in
the range of 0.3 to 3.0% by mass, and preferably 0.5 to 1.5% by
mass.
[0252] When the ink is used with being filled in a ballpoint pen,
it is preferable that the abrasion of a ball receiving sheet is
prevented by adding lubricants including higher fatty acids such as
oleic acid, nonionic surfactants having a long chain alkyl group,
polyether modified silicone oil, thiophosphorous acid triesters
such as thiophosphorous acid tri(alkoxycarbonyl methyl ester) or
thiophosphorous acid tri(alkoxycarbonyl ethyl ester), phosphoric
acid monoester of polyoxyethylene alkyl ether or polyoxyethylene
alkylaryl ether, phosphoric acid diester of polyoxyethylene alkyl
ether or polyoxyethylene alkylaryl ether, and metal salts, ammonium
salts, amine salts and alkanolamine salts thereof.
[0253] The followings may be added to the ink as necessary: resins
which impart the ink with the fixability on the paper surface and
viscosity, such as an acrylic resin, a styrene-maleic acid
copolymer, a cellulose derivative, polyvinylpyrrolidone, polyvinyl
alcohol and dextrin; inorganic salts such as sodium carbonate,
sodium phosphate and sodium acetate; pH regulators, for example, an
organic basic compound such as an aqueous amine compound;
anticorrosives such as benzotriazole, tolyltriazole,
dicyclohexylammonium nitrite, diisopropylammonium nitrite and
saponin; preservatives or fungicides, such as phenol, sodium salt
of 1,2-benzthiazolin-3-one, sodium benzoate, sodium dehydroacetate,
potassium sorbate, paraoxypropyl benzoate and
2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine; wetting agents such
as urea, nonionic surfactant, reduced or non-reduced starch
hydrolysate, oligosaccharides such as trehalose, sucrose,
cyclodextrin, glucose, dextrin, sorbitol, mannitol and sodium
pyrophosphate; defoamers; dispersants; and fluorine-based or
nonionic surfactants which improve the permeability of the ink.
[0254] The ink can contain the microcapsule pigment in the amount
of preferably 5 to 40% by mass, more preferably 10 to 40% by mass,
and still more preferably 10 to 30% by mass, with respect to the
total mass of the ink. By controlling the amount of the
microcapsule pigment in the above range, a desirable coloration
density can be achieved and deterioration of the ink outflow
properties can be inhibited.
[0255] A ballpoint pen and a marking pen, which store the above
ink, will now be described.
[0256] When the ink is filled in a ballpoint pen, the structure and
shape of the ballpoint pen itself are not particularly limited, and
examples thereof include a ballpoint pen having an ink-storing tube
in which a shear-thinning ink is filled in an axial barrel, in
which the ink-storing tube is connected with a ballpoint pen tip
where a ball is mounted on its front-end, and a liquid plug for
preventing backflow is closely contacted in the edge of the ink in
the ink-storing tube.
[0257] The ballpoint pen tip will be described in more detail.
There can be applied a tip formed by holding a ball in a ball
holding part in which the vicinity of a front-end of a metal pipe
is pressed and deformed inwardly from the outside; a tip formed by
holding a ball in a ball holding part formed by cutting a metal
material by a drill and the like; a tip in which a ball receiving
sheet made of a resin is provided in the tip made of metal or
plastic; or a tip in which a ball held in the tip is pressed in a
front direction by a spring.
[0258] It is possible to apply the ball made of cemented carbide,
stainless steel, ruby, ceramic, resin, rubber, and the like, which
has a diameter of about 0.3 to 2.0 mm, preferably 0.3 to 1.5 mm,
and more preferably 0.3 to 1.0 mm.
[0259] It is possible to use, as the ink-storing tube which stores
the ink, for example, a molded body made of a thermoplastic resin
such as polyethylene, polypropylene, polyethylene terephthalate or
nylon or a metal tube.
[0260] The ink-storing tube may be directly connected with the tip,
or the ink-storing tube may be connected with the tip via a
connection member.
[0261] The ink-storing tube may be a refill type in which the
refill is stored in an axial barrel made of a resin or metal, or
the ink may be directly filled in an axial barrel in which the
axial barrel mounting a tip in its front-end is used itself as an
ink-storing tube.
[0262] When the ink is stored in a retractable ballpoint pen, the
structure and shape of the retractable ballpoint pen are not
particularly limited, and any structure can be adopted so long as
the writing front-end provided in the ballpoint pen refill is
received in the axial barrel while being exposed to the atmosphere
and the writing front-end is protruded from the opening part of the
axial barrel by actuation of the in-and-out type mechanism.
[0263] The retractable ballpoint pens can be classified into, for
example, knock-type ballpoint pens, rotation-type ballpoint pens
and slide-type ballpoint pens.
[0264] The knock-type ballpoint pens can take, for example, a
configuration in which a knocking part is arranged on the rear end
or side of the axial barrel and the ballpoint pen tip is projected
from the front-end opening of the axial barrel by pushing the
knocking part, or a configuration in which the ballpoint pen tip is
projected from the front-end opening of the axial barrel by pushing
a clip arranged on the axial barrel.
[0265] The rotation-type ballpoint pens can take, for example, a
configuration in which a rotary part is arranged on a rear part of
the axial barrel and the ballpoint pen tip is projected and
retracted through the front-end opening of the axial barrel by
rotating the rotary part.
[0266] The slide-type ballpoint pens can take, for example, a
configuration in which a slide is arranged on the side of the axial
barrel and the ballpoint pen tip is projected and retracted through
the front-end opening of the axial barrel by operating the slide,
or a configuration in which the ballpoint pen tip is projected and
retracted through the front-end opening of the axial barrel by
sliding a clip arranged on the axial barrel.
[0267] The retractable ballpoint pens may be of a complex type in
which a plurality of ballpoint pen refills are stored in the axial
barrel and the writing end of any one of the ballpoint pen refills
is projected and retracted through the front-end opening of the
axial barrel by the action of a projection-retraction
mechanism.
[0268] An ink backflow preventive is filled at the rear end of the
ink stored in the ink-storing tube.
[0269] The composition of the ink backflow preventive comprises a
non-volatile liquid or a hardly volatile liquid.
[0270] Specific examples thereof include vaseline, spindle oil,
castor oil, olive oil, mineral oil refineries, liquid paraffine,
polybutene, .alpha.-olefine, oligomer or cooligomer of
.alpha.-olefine, dimethyl silicone oil, methylphenyl silicone oil,
amino modified silicone oil, polyether modified silicone oil, and
fatty add modified silicone oil. These liquids can be used alone or
in combination of two or more thereof.
[0271] It is preferable that the viscosity of the non-volatile
liquid and/or hardly volatile liquid is increased to a suitable
viscosity by adding a thickening agent. Examples of the thickening
agent include silica having hydrophobic treated surface;
particulate silica having a methylated surface; aluminum silicate;
swellable mica; a clay-based thickening agent such as
hydrophobically treated bentonite or montmorilonite; fatty acid
metal soaps such as magnesium stearate, calcium stearate, aluminum
stearate, and zinc stearate; a dextrin-based compound such as
tribenzylidene sorbitol, fatty acid amide, amide modified
polyethylene wax, hydrogenated castor oil, or fatty acid dextrin;
and a cellulose-based compound.
[0272] The liquid ink backflow preventive may be used in
combination with a solid ink backflow preventive.
[0273] When the ink is filled in a marking pen, the structure and
shape of the marking pen itself are not particularly limited, and
examples thereof include a marking pen in which an ink occlusion
body made of fiber bundle is embedded in an axial barrel, a marking
pen tip made of a processed fiber having a capillary gap therein is
mounted directly or via a connection member on the axial barrel,
and a cohesive ink is impregnated in the ink occlusion body of the
marking pen formed by connecting the ink occlusion body and the
tip, or a marking pen in which the tip and the ink-storing tube are
arranged through a valve body that opens by pressing the tip and
the ink is directly stored in the ink-storing tube.
[0274] The tip is a generally known porous member having
communication pores of which porosity is selected in the range of
about 30 to 70%, made of processed resin of fibers, fusion
processed bodies of hot-melt fiber, or a felt, and the tip is
provided for practical use by processed its one end in a cannonball
form, a rectangular form, or a chisel form depending on the use
purpose.
[0275] The ink occlusion body is configured by bundling crimped
fibers in a length direction, incorporating them into a covering
material such as a plastic tube or a film, and adjusting its
porosity in the range of about 40 to 90%.
[0276] As the valve body, a generally known pumping type may be
used, and it is suitably a valve body in which a spring pressure is
adjusted so that the valve can be opened by pen pressure.
[0277] The shape of the ballpoint pen or marking pen is not limited
to those mentioned above, and may be a both head type writing
instrument in which tips of different type are provided or pen ends
for introducing inks of different colors are provided.
[0278] When the photochromic liquid composition is coated or
printed, the material of the support is not specified and every
material is effective, and examples thereof include papers,
synthetic papers, fibers, fabrics, synthetic leathers, leathers,
plastics, glasses, pottery materials, metals, woods and stones,
which may be not only in a flat shape but also in an irregular
form.
[0279] A photochromic layer containing a photochromic composition
is arranged on the support to obtain a laminated body (printed
article).
[0280] When a non-photochromic colored layer (including an image)
has been formed on the support in advance, the colored layer can be
made visible or invisible by applying thereto a photochromic layer,
and this enables to further diversify the mode of change.
[0281] The photochromic composition according to the embodiments of
the present invention can also be melt-blended with a thermoplastic
resin, a thermosetting resin, wax or the like into the form of a
pellet, powder or paste and utilized as a resin composition for
photochromic molding. By widely used means such as injection
molding, extrusion molding, blow molding or cast molding, a molded
body in the form of a three-dimensional article of an arbitrary
shape, film, sheet, plate, filament, rod, pipe or the like can be
obtained.
[0282] It is also possible to obtain crayon, pencil core,
mechanical pencil lead, toner and powder paint by melt-blending the
photochromic composition into a thermoplastic resin or wax.
[0283] An ordinarily employed dyestuff or pigment may be added to
the photochromic liquid composition or resin composition for
photochromic molding to cause discoloration behavior from color (1)
to color (2).
[0284] It is possible to improve the light fastness of the product
by laminating a layer containing a light stabilizer and/or a
transparent metalescent pigment on the laminated body or the molded
body formed by using the resin composition for molding, or it is
possible to improve the durability of the product by providing a
topcoat layer thereon.
[0285] Examples of the light stabilizer include ultraviolet
absorbers, antioxidants, singlet oxygen quenchers, superoxide anion
quenchers and ozone quenchers.
[0286] Examples of the transparent metalescent pigment include
pigments prepared by coating the surface of a core substance, such
as natural mica, synthetic mica, glass piece, alumina or
transparent film piece, with a metal oxide such as titanium
oxide.
[0287] Specific examples of products using the photochromic
composition, the microcapsule pigment or the resin particles
include the followings.
(1) Toys:
[0288] dolls or animal-figured toys; hair of dolls or
animal-figured toys; dollhouses and furnitures thereof; doll
accessories such as clothes, hats, bags and shoes; accessory toys;
stuffed dolls and animals; painting toys; illustrated books for
toys; puzzle toys such as jigsaw puzzles; toy bricks; block toys;
clay toys; fluid toys; spinning tops; kites; musical toys; cooking
toys; gun toys; capturing toys; background toys; toys imitating
vehicles, animals, plants, buildings and food articles; and the
like
(2) Clothing:
[0289] outerwears such as T-shirts, sweaters, blouses, dresses,
swimsuits, raincoats and ski wears; footwears such as shoes and
shoelaces; personal effects made of cloth, such as handkerchiefs,
towels and wrapping cloths; gloves; neckties; hats; scarfs;
mufflers; and the like
(3) Interior Ornaments:
[0290] runners, curtains, curtain cords, tablecloths carpets,
cushions, carpets, rugs, chair upholsteries, sheets, mats, picture
frames, imitation flowers, photo stands, and the like
(4) Furnitures:
[0291] beddings such as bedclothes, pillows and mattresses;
lighting fixtures; and the like
(5) Accessories:
[0292] rings, bracelets, tiaras, earrings, hair stoppers,
artificial nails, ribbons, scarfs, watches, glasses, and the
like
(6) Stationeries:
[0293] writing instruments, stamps, erasers, celluloid boards,
rulers, adhesive tapes, and the like
(7) Daily Necessaries:
[0294] cosmetics such as lipsticks, eye-shadows, manicures, hair
dyes, artificial nails and paints for artificial nails;
toothbrushes; and the like
(8) Kitchen Utensils:
[0295] cups, dishes, chopsticks, spoons, forks, pots, frying pans,
and the like
(9) Other Products:
[0296] various printed articles such as calendars, labels, cards,
recording materials and those for forgery prevention; indicators;
books such as illustrated books; bags; packaging containers;
embroidery threads; sporting gears; fishing tackles; coasters;
musical instruments; pouches such as wallets; umbrellas; vehicles;
buildings; training and learning articles; and the like.
EXAMPLES
[0297] While Examples will be illustrated below, the present
invention is not limited thereto. "Part(s)" in the following
Examples are by mass.
Example 1
Preparation of Photochromic Composition
[0298] 1 Part of
3,3,9,9-tetra(4'-sec-butoxyphenyl)-3H,9H-naphtho[2,1-b:6,5-b']-dipyran
was uniformly dissolved in 50 parts of a
styrene-.alpha.-methylstyrene copolymer (manufactured by Eastman
Chemical Company under the trade name of Picolastic A-5) under
heating to obtain a photochromic composition.
Example 2
Preparation of Photochromic Microcapsule Pigment
[0299] After adding 60 parts of the photochromic composition of
Example 1 in a mixed solution comprising 20 parts of an aromatic
isocyanate prepolymer as a film-forming agent and 20 parts of ethyl
acetate, the mixture thus obtained was added dropwise in 100 parts
of an aqueous 15% gelatin solution in such a manner as to form
microdroplets under stirring. Then, the reaction was performed
while heating to prepare a microcapsule dispersion.
[0300] A photochromic microcapsule pigment was obtained from the
microcapsule dispersion by the centrifugal separation method.
[0301] Formulations of the photochromic compositions of Examples 1
to 26, and with or without microcapsulation are shown in Tables 1
to 4 below. Each of the photochromic compositions of Examples 3 to
5 and Examples 10 to 26 was encapsulated in microcapsules in the
same manner as in Example 2 to obtain a photochromic microcapsule
pigment.
[0302] The number in parentheses in the tables indicates parts by
mass.
TABLE-US-00001 TABLE 1 Example 1 2 3 Photochromic
3,3,9,9-Tetra(4'-sec- 3,3,9,9-Tetra(4'-sec- 3,3,9,9-Tetra(4'-sec-
compound butoxyphenyl)-3H,9H- butoxyphenyl)-3H,9H-
butoxyphenyl)-3H,9H- naphtho[2,1-b:6,5-b']- naphtho[2,1-b:6,5-b']-
naphtho[2,1-b:6,5-b']- dipyran (1) dipyran (1) dipyran (1) Oligomer
Styrene-.alpha.-methylstyrene Styrene-.alpha.-methylstyrene
Styrene-.alpha.-methylstyrene copolymer (weight-average copolymer
(weight-average copolymer (weight-average molecular weight of 317)
molecular weight of 317) molecular weight of 317) under the trade
name of under the trade name of under the trade name of Picolastic
A-5 (50) Picolastic A-5 (50) Picolastic A-5 (25) -- --
Styrene-.alpha.-methylstyrene copolymer (weight-average molecular
weight of 917) under the trade name of Picolastic A-75 (25)
Additives -- -- -- With or without Without microcapsulation With
microcapsulation With microcapsulation microcapsulation Example 4 5
6 Photochromic 3,3,9,9-Tetra(4'-sec- 3,3,9,9-Tetra(4'-sec-
3,3,9,9-Tetra(4'-sec- compound butoxyphenyl)-3H,9H-
butoxyphenyl)-3H,9H- butoxyphenyl)-3H,9H- naphtho[2,1-b:6,5-b']-
naphtho[2,1-b:6,5-b']- naphtho[2,1-b:6,5-b']- dipyran (1) dipyran
(1) dipyran (1) Oligomer Acrylic acid ester copolymer Acrylic acid
ester copolymer .alpha.-Pinene polymer (weight- (weight-average
molecular (weight-average molecular average molecular weight of
weight of 1,700) under the weight of 8,000) under the 833) under
the trade name of trade name of ARUFON UP- trade name of ARUFON UP-
Piccolite A115 (50) 1010 (50) 1170 (50) Additives -- -- -- With or
without With microcapsulation With microcapsulation Without
microcapsulation microcapsulation Example 7 8 9 Photochromic
3,3,9,9-Tetra(4'-sec- 3,3,9,9-Tetra(4'-sec- 3,3,9,9-Tetra(4'-sec-
compound butoxyphenyl)-3H,9H- butoxyphenyl)-3H,9H-
butoxyphenyl)-3H,9H- naphtho[2,1-b:6,5-b']- naphtho[2,1-b:6,5-b']-
naphtho[2,1-b:6,5-b']- dipyran (1) dipyran (1) dipyran (1) Oligomer
.beta.-pinene polymer(weight- Styrene-.alpha.-methylstyrene
Styrene-.alpha.-methylstyrene average molecular weight of copolymer
(weight-average copolymer (weight-average 1,710) under the trade
name molecular weight of 317) molecular weight of 317) of Piccolite
S115 (50) under the trade name of under the trade name of
Picolastic A-5 (40) Picolastic A-5 (40) -- .alpha.-Pinene-phenol
copolymer .alpha.-Pinene-phenol copolymer (weight-average molecular
(weight-average molecular weight of 1,050) under the weight of 900)
under the trade name of YS trade name of YS POLYSTAR T145 (10)
POLYSTAR T130 (10) Additives -- -- -- With or without Without
microcapsulation Without microcapsulation Without microcapsulation
microcapsulation
TABLE-US-00002 TABLE 2 Example 10 11 12 Photochromic
3,3,9,9-Tetra(4'-sec- 3,3,9,9-Tetra(4'-sec- 3,3,9,9-Tetra(4'-sec-
compound butoxyphenyl)-3H,9H- butoxyphenyl)-3H,9H-
butoxyphenyl)-3H,9H- naphtho[2,1-b:6,5-b']- naphtho[2,1-b:6,5-b']-
naphtho[2,1-b:6,5-b']- dipyran (1) dipyran (1) dipyran (1) Oligomer
Styrene-.alpha.-methylstyrene Styrene-.alpha.-methylstyrene
Styrene-.alpha.-methylstyrene copolymer (weight-average copolymer
(weight-average copolymer (weight-average molecular weight of 317)
molecular weight of 317) molecular weight of 317) under the trade
name of under the trade name of under the trade name of Picolastic
A-5 (42) Picolastic A-5 (42) Picolastic A-5 (42) Additives
Benzotriazole-based Triazine-based ultraviolet Benzotriazole-based
ultraviolet absorber under the absorber under the trade ultraviolet
absorber under trade name of Tinuvin 928 name of Tinuvin 400 (8)
the trade name of Tinuvin (8) 928 (6) -- -- Hindered amine-based
light stabilizer under the trade name of Tinuvin 765 (2) With or
without With microcapsulation With microcapsulation With
microcapsulation microcapsulation Example 13 Photochromic
3,3,9,9-Tetra(4'-sec- compound butoxyphenyl)-3H,9H-
naphtho[2,1-b:6,5-b']- dipyran (1) Oligomer
Styrene-.alpha.-methylstyrene copolymer (weight-average molecular
weight of 317) under the trade name of Picolastic A-5 (42)
Additives Benzotriazole-based ultraviolet absorber under the trade
name of Tinuvin 928 (6) Hindered amine-based light stabilizer under
the trade name of Tinuvin 144 (2) With or without With
microcapsulation microcapsulation
TABLE-US-00003 TABLE 3 Example 14 15 16 Photochromic
2,2,7,7-Tetra(4'-sec- 2,2,8,8-Tetra(4'-sec- 3,3,8,8-Tetra(4'-sec-
compound butoxyphenyl)-2H,7H- butoxyphenyl)-2H,8H-
butoxyphenyl)-3H,8H- naphtho[1,2-b:4,3-1:1- naphtho[1,2-b:5,6-b']-
naphtho[2,1-b:5,6-b']- dipyran (1) dipyran (1) dipyran (1) Oligomer
Styrene-.alpha.-methylstyrene Styrene-.alpha.-methylstyrene
Styrene-.alpha.-methylstyrene copolymer (weight-average copolymer
(weight-average copolymer (weight-average molecular weight of 317)
molecular weight of 317) molecular weight of 317) under the trade
name of under the trade name of under the trade name of Picolastic
A-5 (50) Picolastic A-5 (50) Picolastic A-5 (50) Additives -- -- --
With or without With microcapsulation With microcapsulation With
microcapsulation microcapsulation Example 17 18 19 Photochromic
2,2,10,10-Tetra(4'-sec- 3,3,6,6-Tetra(4'-sec- 3,3,9,9-Tetra(4'-
compound butoxyphenyl)-2H,10H- butoxyphenyl)-3H,6H-
isopropoxyphenyl)-3H,9H- naphtho[1,2-b:7,8-b']-
naphtho[2,1-b:3,4-b']- naphtho[2,1-b:6,5-b']- dipyran (1) dipyran
(1) dipyran (1) Oligomer Styrene-.alpha.-methylstyrene
Styrene-.alpha.-methylstyrene Styrene-.alpha.-methylstyrene
copolymer (weight-average copolymer (weight-average copolymer
(weight-average molecular weight of 317) molecular weight of 317)
molecular weight of 317) under the trade name of under the trade
name of under the trade name of Picolastic A-5 (50) Picolastic A-5
(50) Picolastic A-5 (50) Additives -- -- -- With or without With
microcapsulation With microcapsulation With microcapsulation
microcapsulation Example 20 21 22 Photochromic 3,3,9,9-Tetra(4'-n-
3,3,9,9-Tetra(4'-n- 3,3,10,10-Tetra(4'-sec- compound
hexyloxyphenyl)-3H,9H- octyloxyphenyl)-3H,9H- butoxyphenyl)-3H,10H-
naphtho[2,1-b:6,5-b']- naphtho[2,1-b:6,5-b']- naphtho[2,1-b:7,8-bT
dipyran (1) dipyran (1) dipyran (1) Oligomer
Styrene-.alpha.-methylstyrene Styrene-.alpha.-methylstyrene
Styrene-.alpha.-methylstyrene copolymer (weight-average copolymer
(weight-average copolymer (weight-average molecular weight of 317)
molecular weight of 317) molecular weight of 317) under the trade
name of under the trade name of under the trade name of Picolastic
A-5 (50) Picolastic A-5 (50) Picolastic A-5 (50) Additives -- -- --
With or without With microcapsulation With microcapsulation With
microcapsulation microcapsulation
TABLE-US-00004 TABLE 4 Example 23 24 25 Photochromic
3,3,10,10-Tetra(4'-sec- 3,3,10,10-Tetra(4'-sec-
3,3,10,10-Tetra(4'-sec- compound butoxyphenyl)-3H,10H-
butoxyphenyl)-3H,10H- butoxyphenyl)-3H,10H- naphtho[2,1-b:7,8-b']-
naphtho[2,1-b:7,8-b']- naphtho[2,1-b:7,8-b']- dipyran (1) dipyran
(1) dipyran (1) Oligomer Styrene-.alpha.-methylstyrene
Styrene-.alpha.-methylstyrene Styrene-.alpha.-methylstyrene
copolymer (weight-average copolymer (weight-average copolymer
(weight-average molecular weight of 317) molecular weight of 317)
molecular weight of 317) under the trade name of under the trade
name of under the trade name of Picolastic A-5 (42) Picolastic A-5
(42) Picolastic A-5 (42) Additives Benzotriazole-based
Triazine-based ultraviolet Benzotriazole-based ultraviolet absorber
under the absorber under the trade ultraviolet absorber under trade
name of Tinuvin 928 name of Tinuvin 400 (8) the trade name of
Tinuvin (8) 928 (6) -- -- Hindered amine-based light stabilizer
under the trade name of Tinuvin 765 (2) With or without With
microcapsulation With microcapsulation With microcapsulation
microcapsulation Example 26 Photochromic 3,3,10,10-Tetra(4'-sec-
compound butoxyphenyl)-3H,10H- naphtho[2,1-b:7,8-b']- dipyran (1)
Oligomer Styrene-.alpha.-methylstyrene copolymer (weight-average
molecular weight of 317) under the trade name of Picolastic A-5
(42) Additives Benzotriazole-based ultraviolet absorber under the
trade name of Tinuvin 928 (6) Hindered amine-based light stabilizer
under the trade name of Tinuvin 144 (2) With or without With
microcapsulation microcapsulation
[0303] Formulations of the photochromic compositions of Comparative
Examples 1 to 4, and with or without microcapsulation are shown in
Table 5 below. Each of the photochromic compositions of Comparative
Examples 1 to 4 was encapsulated in microcapsules in the same
manner as in Example 2 to obtain a photochromic microcapsule
pigment.
[0304] The number in parentheses in the tables indicates parts by
mass.
TABLE-US-00005 TABLE 5 Comparative Example 1 2 3 Photochromic
3,3,9,9-Tetra(4'- 3,3,6,6-Tetra(4'- 3,3,9,9-Tetraphenyl-3H,9H-
compound methoxyphenyl)-3H,9H- methoxyphenyl)-3H,6H-
naphtho[2,1-b:6,5-b']- naphtho[2,1-b:6,5-b']-
naphtho[2,1-b:3,4-b']- dipyran (1) dipyran (1) dipyran (1) Oligomer
Styrene-.alpha.-methylstyrene Styrene-.alpha.-methylstyrene
Styrene-.alpha.-methylstyrene copolymer (weight-average copolymer
(weight-average copolymer (weight-average molecular weight of 317)
molecular weight of 317) molecular weight of 317) under the trade
name of under the trade name of under the trade name of Picolastic
A-5 (50) Picolastic A-5 (50) Picolastic A-5 (25) Additives -- -- --
With or without With microcapsulation With microcapsulation With
microcapsulation microcapsulation Comparative Example 4
Photochromic 3,3,10,10-Tetra(4'- compound methoxyphenyl)-3H,10H-
naphtho[2,1-b:7,8-b']- dipyran (1) Oligomer
Styrene-.alpha.-methylstyrene copolymer (weight-average molecular
weight of 317) under the trade name of Picolastic A-5 (50)
Additives -- With or without With microcapsulation
microcapsulation
Fabrications of Test Samples
[0305] Each of the photochromic compositions of Examples 1 to 26
and Comparative Examples 1 to 4 was dissolved in 100 parts of
methyl ethyl ketone. The solution thus obtained was coated on a
white synthetic paper using a bar coater so that the wet film
thickness became 90 .mu.m, followed by drying to obtain a test
sample.
Color Tone Test
[0306] After each of the above test samples was irradiated with
light from a light source [bulb-shaped fluorescent lamp
manufactured by Toshiba Lighting & Technology, Corporation
under the trade name of Neoball 5 Black Light EFD15BLB] placed 10
cm apart from the sample for 1 minute, the color tone at the time
of coloration was visually confirmed. Furthermore, the color tone
at the time of decolorization was visually confirmed.
Brightness Value Test
[0307] After each of the above test samples was irradiated with
light from the light source placed 10 cm apart from the sample for
1 minute, the brightness value (converted from Y value) was
measured by a color-difference meter [TC-3600 manufactured by Tokyo
Denshoku Co., Ltd.]. Furthermore, the brightness value (converted
from Y value) at the time of decolorization was measured by the
color-difference meter.
[0308] The larger the brightness value is, the lower is the color
density. The smaller the brightness value is, the higher is the
color density.
Decolorization Speed Test
[0309] After each of the above test samples was irradiated with
light from the light source placed 10 cm apart from the sample for
1 minute to develop a color, the time until decolorization
(reaching the initial density) was measured.
Light Fastness Test
[0310] After each of the above test samples was continuously
irradiated with light using a xenon light fastness tester [Table
Sun XT75 manufactured by Suga Test Instruments Co., Ltd.] at an
irradiance of 170 w/m.sup.2 under a temperature environment of
35.degree. C.
[0311] Each of the above test samples was taken out every 5 hours
and irradiated with light from the light source to develop a color,
and then the presence or absence of a discoloration function was
confirmed, and the time during which the discoloration function
disappeared was measured.
[0312] The results of the color tone test, the brightness value
test, the decolorization speed test and the light fastness test of
each of the test samples are shown in Tables 6 and 7 below.
TABLE-US-00006 TABLE 6 Color tone test Brightness value test At the
time of At the time of At the time At the time of Decolorization
Light Example coloration decolorization of coloration
decolorization speed test fastness test 1 Red White 6.62 9.22 170
seconds 10 hours 2 Red White 6.05 8.90 150 seconds 10 hours 3 Red
White 5.71 9.01 200 seconds 10 hours 4 Red White 7.67 8.99 100
seconds 10 hours 5 Red White 7.52 8.99 90 seconds 10 hours 6 Red
White 7.46 9.22 30 minutes or more 10 hours 7 Red White 7.00 9.23
30 minutes or more 10 hours 8 Red White 6.07 8.92 200 seconds 10
hours 9 Red White 6.21 8.96 200 seconds 10 hours 10 Red White 6.29
9.03 140 seconds 45 hours 11 Red White 5.71 9.01 120 seconds 20
hours 12 Red White 6.84 9.05 140 seconds 65 hours 13 Red White 6.36
9.04 180 seconds 65 hours 14 Orange White 6.51 8.99 200 seconds 10
hours 15 Red White 6.87 8.99 170 seconds 10 hours 16 Red White 6.54
9.01 150 seconds 10 hours 17 Orange White 8.17 9.00 50 seconds 15
hours 18 Orange White 6.83 8.88 300 seconds 5 hours 19 Red White
6.33 8.85 120 seconds 10 hours 20 Red White 6.45 8.82 150 seconds
10 hours 21 Red White 6.67 8.90 130 seconds 10 hours 22 Orange
White 8.24 8.99 40 seconds 15 hours 23 Orange White 8.68 9.00 30
seconds 60 hours 24 Orange White 8.28 9.04 40 seconds 30 hours 25
Orange White 8.94 9.10 40 seconds 120 hours 26 Orange White 8.89
9.06 30 seconds 120 hours
TABLE-US-00007 TABLE 7 Color tone Brightness value test Comparative
At the time of At the time of At the time of At the time of
Decolorization Light fastness Example coloration decolorization
coloration decolorization speed test test 1 Red White 7.81 9.04 80
seconds 10 hours 2 Orange White 7.48 8.90 100 seconds 5 hours 3
Orange White 6.74 9.01 600 seconds 5 hours 4 Yellow White 8.91 9.02
10 seconds 15 hours
Application Example 1
Fabrication of Photochromic Display
[0313] 10 Parts of the photochromic composition of Example 1 was
mixed with 10 parts of toluene to prepare a photochromic liquid
composition. A transparent polypropylene sheet was coated with the
photochromic liquid composition using a wire coater in a wet film
thickness of 50 .mu.m, and after drying to provide a photochromic
layer, a white paper was laminated thereon to obtain a photochromic
display.
[0314] When viewed from the transparent polypropylene sheet side,
the photochromic display was white before exposure to sunlight, but
turned red when exposed to sunlight. Thereafter, when the
photochromic display was left indoors for a while, it returned to
its original white color.
Application Example 2
Fabrication Photochromic Ballpoint Pen
[0315] 27.0 Parts of the photochromic microcapsule pigment of
Example 2, 0.25 part of succinoglycan (organic acid-modified
heteropolysaccharide whose constituent monosaccharides are glucose
and galactose, shear-thinning tackifier), 10.0 parts of glycerin,
0.2 part of a fungicide [manufactured by Zeneca Inc. under the
trade name of Proxel XL-2], 0.1 part of a defoamer [manufactured by
SAN NOPCO Ltd. under the trade name of Nopco 8034] and 2.0 parts of
a lubricant [manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. under
the trade name of PLYSURF DB-01 (neutralized phosphoric acid
ester)] were uniformly dispersed by stirring in 60.45 parts of
water to obtain a photochromic ink for writing instrument.
[0316] After suction-filling 0.8 g of the photochromic ink for
writing instrument into an ink-storing tube made of polypropylene,
a holder made of a resin that holds a ballpoint pen tip holding a
cemented carbide ball having a diameter of 0.8 mm at the tip of a
stainless steel pipe was connected to the ink-storing tube. A
viscoelastic ink backflow preventive (liquid plug) containing
polybutene as a main component was filled at the rear of the ink,
subjected to a centrifugal treatment and then assembled in an axial
barrel to obtain a photochromic ballpoint pen.
[0317] When writing on JIS P3201 writing paper A under room light
using the photochromic ballpoint pen, the handwriting was
colorless, but when exposed to sunlight, it developed a red color.
Thereafter, when the handwriting was left indoors for a while, it
returned to its original colorlessness.
[0318] The photochromic ballpoint pen had high writing performance
as a ballpoint pen without causing line skipping.
Application Example 3
Fabrication of Photochromic Toy
[0319] 20 Parts of the photochromic microcapsule pigment of Example
4 was mixed with 30 parts of an acrylic resin/xylene solution, 20
parts of xylene, 20 parts of methyl isobutyl ketone and 10 parts of
an isocyanate-based curing agent to prepare a photochromic spray
paint. On the surface of a miniature car in which an ABS resin
colored in yellowish green was injection-molded as a support, a
photochromic layer was provided using the photochromic spray paint
to obtain a photochromic toy.
[0320] The photochromic toy was yellowish green before exposure to
sunlight, but turned brown when exposed to sunlight. Thereafter,
when the photochromic toy was left indoors for a while, it returned
to its original yellowish green.
[0321] When the photochromic toy was irradiated with light using a
light irradiator equipped with an LED (peak emission wavelength 430
nm) as a light source at the tip, the irradiated portion changed
from yellowish green to brown. After that, when the photochromic
toy was left for a while, it returned to the original yellowish
green color. This color change could be repeated. Since the above
light source has a peak emission wavelength of 430 nm and
irradiates blue light, it has little effect on the human body and
is a highly safe toy.
Application Example 4
[0322] Fabrication of Doll Toy with Hairs Using Photochromic
Composite Fibers
[0323] 5 Parts of the photochromic microcapsule pigment of Example
12, 1 part of a dispersant, 94 parts of nylon 12 having a melting
point of 180.degree. C. and 0.1 part of a common blue pigment were
melt-mixed with an extruder at 200.degree. C. to prepare
photochromic pellets for core part.
[0324] Photochromic pellets were fed into a core-forming extruder
and nylon 12 natural pellets were fed into a sheath-forming
extruder, respectively. Using a composite-fiber spinning apparatus,
these materials were spun through ejection orifices with 18 holes
at 200.degree. C. in a core-sheath volume ratio of 6:4 to prepare a
photochromic composite fiber composed of 18 single yarns having an
outer diameter of 90 .mu.m.
[0325] The photochromic composite fibers were transplanted to the
head of the doll by a conventional method to obtain a doll toy with
hairs using the photochromic composite fibers.
[0326] The hair of a doll toy was blue before exposure to sunlight,
but turned purple when exposed to sunlight. Thereafter, when the
doll toy was left indoors for a while, it returned to its original
blue color.
[0327] When the hair of the doll toy was irradiated with light
using a light irradiator equipped with an LED (peak emission
wavelength of 430 nm) as a light source at the tip, the irradiated
portion changed from blue to purple.
[0328] Thereafter, when the doll toy was left for a while, it
returned to its original blue color. This color change could be
repeated. Since the above light source has a peak emission
wavelength of 430 nm and irradiates blue light, it has little
effect on the human body and is a highly safe toy.
Application Example 5
Fabrication of Photochromic Molded Body
[0329] 75 Parts of the photochromic microcapsule pigment of Example
18 and 750 parts of medium- and low-pressure polyethylene were
mixed, and then the mixture was extruded at a molding temperature
of 160.degree. C. to 170.degree. C. using an extruder and
pelletized by a pelletizer to prepare photochromic pellets.
[0330] Using the photochromic pellets, a 1 mm thick photochromic
molded body was obtained using an injection molding machine at a
setting temperature of 160.degree. C. to 170.degree. C.
[0331] The photochromic molded body was white before exposure to
sunlight, but turned orange when exposed to sunlight. Thereafter,
when the photochromic molded body was left indoors for a while, it
returned to its original white color.
Application Example 6
Fabrication of Photochromic Printed Matter
[0332] 40 Parts of the photochromic microcapsule pigment of Example
22 was uniformly mixed in a vehicle comprising 58 parts of an
ethylene-vinyl acetate copolymer resin emulsion, 3 parts of a
defoamer, 1 part of a thickener, 3 parts of a leveling agent and 1
part of a preservative to prepare a photochromic screen ink.
[0333] On a white synthetic paper as a support, a photochromic
layer with a star pattern was provided by screen printing using the
photochromic screen ink to obtain a photochromic printed
matter.
[0334] The photochromic printed matter was white before exposure to
sunlight, but when exposed to sunlight, an orange star pattern
appeared. Thereafter, when the photochromic printed matter was left
indoors for a while, the star pattern disappeared and returned to
the original white color.
[0335] This application claims priority based on Japanese Patent
Application 2018-244604 filed on Dec. 27, 2018, the disclosure of
which is incorporated by reference herein.
* * * * *